Iron-promoted hydroxylation of n-Butane by O2

The development of efficient and selective hydrocarbon oxidation processes under mild and environmentally benign conditions remains a major challenge of the 21st century. In an effort to mimic nonheme iron enzymes that activate O2 to functionalize strong substrate C–H bonds, Graduate Student Scott Kleespies and Post-Doctoral Associate Williamson Oloo, Ph.D., in the research group of Professor Lawrence Que Jr., have demonstrated the hydroxylation of n-butane under ambient conditions by the reaction of O2 with an iron complex that mimics the active site of the enzyme TauD.

This work was stimulated by the doctorate thesis of Anusree Mukherjee, who laid the foundation for this achievement. It is proposed that the activation of O2 by the iron(II) complex generates a high-spin FeIV=O oxidant capable of cleaving strong C–H bonds.

This first example of the oxidation of a light alkane by a nonheme oxoiron(IV) complex is published online in Inorganic Chemistry (DOI: 10.1021/ic502786y). It serves as a steppingstone toward a greater understanding of how metalloenzymes work and highlights the potential such synthetic systems may hold.

Anusree Mukherjee earned her doctorate in 2011 under the tutelage of Professor Que, and is an assistant professor at the University of Alabama in Huntsville.